Synthesis and properties of novel amphiphilic sulfated ionomers by the ring‐opening reaction of an epoxidized styrene–butadiene–styrene triblock copolymer

A method for the synthesis of novel sulfated ionomer of styrene–butadiene–styrene triblock copolymer (SBS) was developed. SBS was first epoxidized by performic acid in the presence of a phase‐transfer catalyst; this was followed by a ring‐opening reaction with an aqueous solution of alkali salt of bisulfate. The optimum conditions for the ring‐opening reaction of the epoxidized SBS with an aqueous solution of KHSO₄ were studied. During the ring‐opening reaction, both phase‐transfer catalyst and ring‐opening catalyst were necessary to enhance the conversion of epoxy groups to ionic groups. The products were characterized with Fourier transform infrared spectrophotometry and transmission electron microscopy (TEM). After the potassium ions of the ionomer were substituted with lead ions, the lead sulfated ionomer exhibited dark spots under TEM. Some properties of the sulfated ionomer were studied. With increasing ionic groups or ionic potential of the cations, the water absorbency and emulsifying volume of the ionomer and the intrinsic viscosity of the ionomer solution increased, whereas the oil absorbency decreased. The sulfated ionomer possessed excellent emulsifying properties compared with the sulfonated SBS ionomer. The sodium sulfated ionomers in the presence of 10% zinc stearate showed better mechanical properties than the original SBS. When the ionomer was blended with crystalline polypropylene, a synergistic effect occurred with respect to the tensile strength. The ionomer behaved as a compatibilizer for blending equal amounts of SBS and oil‐resistant chlorohydrin rubber. In the presence of 3% ionomer, the blend exhibited much better mechanical properties and solvent resistance than the blend without the ionomer. SEM photographs indicated improved compatibility between the two components of the blend in the presence of the ionomer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of a novel proton‐exchange membrane for fuel cells operating at high temperatures and low humidities

The synthesis of a p‐toluidine/formaldehyde (PTF) resin was performed, and the effects of the molar ratio of the individual monomers and the polymerization conditions on the structure of the PTF resin were studied. Fourier transform infrared and ¹³C‐NMR spectra were used to characterize the PTF. Wide‐angle X‐ray diffraction patterns revealed the crystalline structures of various PTFs. Polarized optical microscopy revealed that the molar ratio of the monomers had a strong effect on the crystalline morphologies. A longer polymerization time turned out a polymer with a higher intrinsic viscosity and molecular weight, which led to differences in the proton conductivity. All of the PTFs showed a higher proton conductivity than a commercial Nafion membrane at 90–100°C and 0% relative humidity. The proton conductivity of the PTF series could be improved by sulfonation with sulfuric acid and could be maintained after blending with polyurethane. Pure methanol could be used as a fuel source because of the insolubility and nonwetting properties of PTF in methanol to increase the output current density for a PTF membrane electrode assembly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Water and salt permeability of reinforcement polymer‐gel composite membrane

The charged mosaic polymer membrane (CMM) without reinforcement and the composite charged mosaic polymer membrane (CCMM) with reinforcement were investigated in terms of salt and water transport (permeability). The composite charged mosaic polymer membrane (CCMM) with reinforcement showed a unique transport behavior such as preferential material transport L_p and ω. Water permeability coefficient, L_p and salt permeability coefficient, ω were estimated by taking account of active layer thickness of composite polymer gel. The L_p and ω values of CCMM with reinforcement were larger than those of CMM without reinforcement. On the other hand, the reflection coefficient of CCMM, σ, showed negative value, which suggested preferential material transport to solvent transport. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology

The use of phosphazene bases in combination with water was proved to be efficient in order to obtain polysiloxane polymers from cyclic monomers. Only a few minutes are necessary to obtain polymer chains with a monomer concentration of 5% at the equilibrium. For that purpose the space which is between a rheometer's plates is the most convenient device to monitor this reaction concerning a chemical and viscoelastic point of view. Therefore, here is proposed a chemo-rheology study that leads in the same time to the chemical kinetics equations and to the variation of the viscoelastic functions during the polymerization. In this way different catalysts are used and their efficiencies are compared as a function of their “basicity tank”. Whatever the experimental conditions involved are, viscosity versus polymer concentration or conversion shows a master curve for catalysts suitable to be used under extrusive conditions. Thus, only a few experiments are needed in order to develop a model which can be used to foresee the variation of the viscosity during the reaction.     

Accelerated wear testing with a microfabricated surface to evaluate the lubrication ability of biomolecules on polyethylene

Wear of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and wear‐particle‐induced osteolysis and bone resorption are the major factors causing the failure of total joint replacements. It is feasible to improve the lubrication and reduce the wear of artificial joints. We need further understanding of the lubrication mechanism of the synovial fluid. The objective of this study is to evaluate the lubricating ability of three major components in the synovial fluid: albumin, globulin, and phospholipids. An accelerated wear testing procedure in which UHMWPE is rubbed against a microfabricated surface with controlled asperities has been developed to evaluate the lubrication behavior. An analysis of the wear particle dimensions and wear amount of the tests has provided insights for comparing their lubrication performance. It is concluded that the presence of biomolecules at the articulating interface may reduce friction. A higher concentration of a biological lubricant leads to a decrease in the wear particle width. In addition, in combination with the wear results and mechanical analysis, the roles of individual biomolecules contributing to friction and wear at the articulating interface are discussed. These results can help us to identify the role of the biomolecules in the boundary lubrication of artificial joints, and further development of lubricating additives for artificial joints may be feasible. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Water absorption properties of phosphate glass fiber‐reinforced poly‐ϵ‐caprolactone composites for craniofacial bone repair

The moisture uptake of polymers and composites has increasing significance where these materials are specified for invasive, long‐term medical applications. Here we analyze mass gain and the ensuing degradation mechanisms in phosphate glass fiber reinforced poly‐?‐caprolactone laminates. Specimens were manufactured using in situ polymerization of ?‐caprolactone around a bed of phosphate glass fibers. The latter were sized with 3‐aminopropyltriethoxysilane to control the rate of modulus degradation. Fiber content was the main variable in the study, and it was found that the moisture diffusion coefficient increased significantly with increasing fiber volume fraction. Diffusion, plasticization, and leaching of constituents appear to be the dominant aspects of the process over these short‐term tests. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Isothermal crystallization behavior of hybrid biocomposite consisting of regenerated cellulose fiber,clay, and poly(lactic acid)

Quantitative analysis of isothermal crystallization kinetics of PLA/clay nanocomposite and PLA/clay/regenerated cellulose fiber (RCF) hybrid composite has been conducted. The crystallization rate constant (k) according to Avrami equation was higher in PLA/clay nanocomposite than in PLA/clay/RCF hybrid composite at the same crystallization temperature. The equilibrium melting temperature obtained by Hoffman–Weeks equation was almost same in both composites, whereas stability parameter was greater in hybrid composite than in nanocomposite. Activation energy of hybrid composite for crystallization was larger than that of nanocomposite. The value of nucleation parameter (K_g) and surface free energy (s_e) of hybrid composite were larger than nanocomposite, indicating that hybrid composite has a less folding regularity than nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetic study of the decompositions involved in the thermal degradation of commercial azodicarbonamide

The transitions and reactions involved in the thermal treatment of several commercial azodicarbonamides (ADC) in an inert atmosphere have been studied by dynamic thermogravimetry analysis (TGA), mass spectrometry and Fourier transform infrared (FTIR) spectroscopy. A pseudo‐mechanistic model, involving several competitive and non‐competitive reactions, has been suggested and applied to the correlation of the weight loss data. The model applied is capable of accurately representing the different processes involved, and can be of great interest in the understanding and quantification of such phenomena, including the simulation of the instantaneous amount of gases evolved in a foaming process. In addition, a brief discussion on the methodology related to the mathematical modeling of TGA data is presented, taking into account the complex thermal behaviour of the ADC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008